Sulphur resins and methods of preparation



- Patented Mar. 24, 1936 UNITED STATES SULPHUR RESINS ANDMETHODS OF PREPARATION William Seaman, Glens Falls, N. Y., assignor to Standard Oil Development Company No Drawing. Application November 16, 1931, Serial No. 575,466

Claims. (01. zoo-2) This invention relates to new resins containing sulphur and to methods of preparation thereof and more particularly to the use of organic sulphur compoundssuch as those obtainable from petroleum and their derivatives in the preparation of resins.

It is known that resins may be prepared by the condensation of resiniphore substances with oxygen-containing organic compounds, particularly hydroxy compounds suchas phenol, cresol, resor cinol and the like by application of heat, pressure, catalysts such as strong acids or bases or resinifying agents such as the sulphur chlorides. Olefines, aldehydes and ketones may also be added with the above hydroxy compounds and resins of widely varying properties may be there by obtained. Turpentine or pine oil and rosin may also be converted into improved or modified resins with sulphuric acid and/or phenol, formaldehyde and other known conditions favoring resin formation.

It has now been found that organic compounds containing sulphur such as mercaptans, thicethers, disulphides, polysulphides, sulphoxides, sulphones, sulphinic or sulphonic acids, and in general the sulphur-containing compounds or derivatives thereof occurring in or obtained from petroleum, may be used in combinations of, the

above resin forming processes and new types of resins 'may be thereby obtained. All such compounds contain the radical RS corresponding to the petroleum mercaptans from which they 7 are derived. R indicates the hydrocarbon radical of the petroleum mercaptans. Mixtures of'such organic compounds containing sulphur suitable for this invention may be prepared from the mixtures of mercaptans extracted from petroleum and accordingly contain RS- groups corresponding to such mixtures of mercaptans. For example, these organic sulphur compounds inay be used in preparing resins with aromatic hydroxy C. is mixed with an'equal part of phenol and the resulting mixture is treated with an excess of sulphur monochloride and warmed sufiiciently to start reaction. By this process a resin is obtained whose hardness depends upon the degreeof heating, relatively soft resins being obtained on heating at temperatures below to 0., resins of increasing hardness being formed at' higher temperatures and substantially infusible 5 and insoluble resins being obtained on prolonged heating at temperatures of to C. or above. In place of sulphur monochloride in the above reaction the dichloride may be used or free flowers of sulphur may even beused in addition 10 or in substitution for the chloride. Other compounds such as the naphthols, cresols, chlorphenols and the like, resorcinol, pine oil or resin and similar substances may be used-in addition or in substitution for the phenol. Phenol and 15 formaldehyde maybe reacted in the presence of organicsulphur compounds derived from petroleum. In general, resins of the soluble-andfusible types, including cracking coil tar resins as prepared in co-pending applications5'i2,05859-.6O 20 and 572,228, may also betreated with these organic sulphur compounds. The other organic sulphur compounds already mentioned may be used in addition to or in substitution for the mercaptans. For example, the polysulphides such as 5 methyl, ethyl and pr'opyl tri, tetra or penta Sui-- phides or similar alkyl, aryl or mixed polysulphides, are particularly desirable for preparing phenol-sulphur resins. In the preparation of these resins the organic sulphides may act simply 0 as mutual solvents for the reagents and resins formed, or they may act as a source of sulphur or 'may enter more or less completely as reagents into the finished resins.

The solubility of the resins will naturally vary 35 widely depending upon the other reagents used r and other characteristics are similar to-those of 40 resins prepared by known corresponding methods with the addition of other organic compounds, one of the chief advantages of using the organic sulphur compounds being their cheapness and ready availability from petroleum oils.

ample, the thio-ethers may be prepared by passing the mercaptans already described over suitable metallic sulphide catalysts as described in the cc-pendingapplication No. 585,156 filed January' 6, 1932 by Seaman and Hufiman. The di- 5 sulphides may be prepared by limited oxidation of the spent aqueous caustic solution used for treating petroleum naphthas as described in the co-pending application Ser. No. 537,175 filed May 13, 1931 by H. G. M. Fischer now Patent 2,001,715. 55

For ex- 45 oleflnic hydrocarbons; sulphur chloride and sulsulphides may be prepared from either the thioethers or disulphides'by reaction with metallic polysulphides or by other known methods. These organic sulphur compounds: are usually obtained as complex mixtures irom petroleum and may be used as obtained or after separation by suitable means into pure compounds. This invention includes generally both aryl, alkyl and mixed sulphur compounds of the types already described which are defined for the purpose of this invention as organic sulphur compounds derivable from the sulphur compounds of petroleum.

The resins prepared according to my invention are suitable for use in substitution for other known resins of similar characteristics such as solubility, fusibility, and hardness. These resins may be used in coating compositions such as spirit varnishes, oil varnishes, paints and the like, and in the preparation-of moulded articles generally. The resins may be mixed with plasticizing substances and fillers such as camphor, glycerol,-

rubber, nitro-cellulose, asbestos, mica, silica, wood flour and the like. The resins prepared at higher temperatures and 'being substantially iniusible and insoluble are simlar to the resinoids such as bakelite C and have similar uses.

My invention is not to be limited to any examples given illustratively .nor to any theory or the reaction of these sulphur compounds in forming resins, but only by the following claims in which I wish to claim all novelty insofar as the prior art permits.

I claim:

1. Method of preparing a resin containing sul- I phur, comprising heating a mixture 01' an aromatic hydroxy compoundhaving a hydroxy group attached to the nucleus, with a substance capable I of reaction therewith to form resins and selected from the group consisting of aldehydes, ketones,

phur, and with. a mixture of organic sulphur compounds containing RS groups, corresponding to the mixture of mercaptans present in'petrolum, in which R. indicates a hydrocarbon radical of such mercaptans.

2. The product of the processor claim 1.

3. In the preparation of synthetic resins containing sulphur by reaction of aromatic hydroxy compounds having a hydroxy group attached to the nucleus, with a chloride of sulphur, the improvement comprising substituting for a part of said hydroxy compound'a mixture 01 organic sulphur compounds containing RS- groups corresponding to the mixture or mercaptans present in petroleum, in which R indicates a hydrocarbon radical or such mercaptans.

4. A sulphur containing resin prepared by reaction of a phenol, a chloride of sulphur, and an organic sulphur compound containing RS groups corresponding to the mixture of mercaptans present in petroleum, in which R indicates a hydrocarbon radical of such mercaptans.

' 5. Method of preparing a resin containing sulphur comprising heating a mixture of phenol and sulphur monochloride with a. mixture of mercaptans corresponding to the mixture of mercaptans in a petroleum oil. 7

6. Method according to claim 5, in which the reaction is carried out by heating at temperatures below C.

7. Method according to claim 5, in which the reaction is carried out by heating at temperatures of to C.

8. Method of preparing a resin containing sulphur which comprises heating a mixture or about one part of mercaptans obtained from light cracked petroleum naphthas and freed from comp nents boiling below 40 0., about one part oiphenol and an excess of sulphur monochloride.

9. A sulphur containing resin prepared by reaction of a composition comprising phenol, sulextracted from a petroleum oil. I 9

10., Method of preparing a resin containing sulphur comprising heating -a mixture of phenol and leum, in which R indicates a hydrocarbon radical of such mercaptans.

phur monochloride, and a mixtin'e of mercaptans 

